CN104897735B - A kind of photocatalysis formula formaldehyde sensor of double-decker and preparation method thereof - Google Patents
A kind of photocatalysis formula formaldehyde sensor of double-decker and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to a kind of photocatalysis formula formaldehyde sensor with double-decker and preparation method thereof.The formaldehyde sensor includes light source, electrode, formaldehyde sensitive material and methyl aldehyde adsorption material layer, and on the electrodes, the methyl aldehyde adsorption material layer is covered on the formaldehyde sensitive material for the formaldehyde sensitive material covering.Preferably, formaldehyde sensitive material is cadmium doped zinc oxide nano particle, and methyl aldehyde adsorption material layer is porous oxidation nano silicon particles.The light source is ultraviolet source, is irradiated to the double-decker region.When detecting the formaldehyde pollutants in air, methyl aldehyde adsorption material layer can increase the concentration of formaldehyde of formaldehyde sensitive material layer surface, so as to increase sensor sensitivity, i.e., can improve the sensitivity for low concentration formaldehyde.Sensitivity of the cadmium doping zinc-oxide formaldehyde sensor for low concentration formaldehyde greatly improved in the present invention, has promoted the practical progress of the sensor, has had a good application prospect.
Description
Technical field
The invention belongs to formaldehyde gas monitoring, formaldehyde sensor technical field, and in particular to a kind of light of double-decker is urged
Change formula formaldehyde sensor and preparation method thereof.
Background technology
The formaldehyde gas that Long Term Contact exceedes safe concentration limitation is very harmful to health, and this may cause eyes
With the burning sensation of throat, expiratory dyspnea even can cause fatal disease, such as rhinocarcinoma, myelomatosis etc..At present in
State's formaldehyde pollution is still very serious, and nearly 70% newly-decorated house is all perplexed by formaldehyde pollution, therefore is most made in China
The indoor polluted gas that people worries is exactly formaldehyde.
For air quality product, the technology of sensor is very important, if because the uncertain sky of consumer
The true effect of gas quality product, then they will throw doubt upon to Related product.If current commercialized sensor main
Based on electrochemical type sensor, this kind of sensor becomes very expensive due to using platinum electrode, in addition this kind of sensor
Accuracy, stability and selectivity it is all not fully up to expectations.
To be compared with electrochemical sensor, semiconductor transducer has its special advantage, including cost is low, long lifespan etc., and
And there is huge room for promotion.Current commercial sensor is required for working more than 200 DEG C, and the almost institute in this temperature
Some organic pollutions can react and detect, so the selectivity of this kind of sensor is excessively poor.In order to improve to gas
Selectivity, part researcher are also made that the photocatalytic semiconductor formaldehyde sensor to work at room temperature, but for application
For these sensors Monitoring lower-cut (being more than 1ppm) it is still very high.Table 1 list some existing sensing materials with
And its problem of existing.
1. existing sensing material of table
Patent application CN2007153341 (formaldehyde air sensing material and formaldehyde air sensing equipment preparation method) is related to
To formaldehyde gas sensing material and preparation method thereof, include the preparation method of formaldehyde gas sensor part.The sensing material is
By SnO2-TiO2Bielement nano powder constituent, Ti/Sn mol ratio is 0.2-0.5, and mixes 2%-5% cadmium, by material with
It is then uniformly coated onto on electrode tube to pasty state, electrode tube is moved back at 400 DEG C by absolute ethyl alcohol and polyethylene glycol co-ground
Formaldehyde gas sensor can obtain by welding, aging, sealing after fiery 2-4 hours.The sensor operations temperature is low, PARA FORMALDEHYDE PRILLS(91,95)
High sensitivity and there is very strong antijamming capability for indoor polluted gas such as benzene,toluene,xylene, ammonia, and have
There is the characteristics of very short response time and turnaround time.The sensor is mainly used in detecting formaldehyde gas caused by interior decoration.
But the operating temperature of the sensor is 260-300 DEG C, almost all of indoor organic pollutant can pass at such a temperature
Sense material surface is oxidized, so the selectivity of material is not fully up to expectations, can not particularly distinguish ethanol and formaldehyde well.This
The detection limit of the outer technology is 20ppm, and this is higher by two orders of magnitude than safe concentration (0.06ppm).
Patent application CN201410461045.9 (a kind of photocatalysis formaldehyde sensing material and its synthetic method and formaldehyde sensing
Device) it is related to a kind of photocatalysis formaldehyde sensing material and its synthetic method and formaldehyde sensor.Photocatalysis formaldehyde sensing material master
To be made up of Zinc oxide nanoparticle and cadmium additive.During synthesizing the material, first by pre-synthesis zinc oxide
Nano particle is dispersed in cadmium salt soln, is stirred simultaneously solvent evaporated simultaneously, will be ground after obtained sediment high-temperature calcination
And be dispersed in specific solvent and form slurry, finally slurry is coated with the electrode for be printed on specific pattern so as to obtain first
Aldehyde sensor.This solution provides a kind of low cost, high sensitivity, high selectivity photocatalysis formaldehyde sensing material, by excellent
Incorporation of the cadmium in zinc oxide, greatly reduces cost, improves selectivity, and significantly improve detection limit.Though however,
The Monitoring lower-cut of formaldehyde is fallen below 0.5ppm by the right technology, but is still higher by nearly quantity than safe concentration (0.06ppm)
Level, is unsuitable for the practical application in living environment.
The content of the invention
The present invention is in view of the above-mentioned problems, provide a kind of with the photocatalysis formula formaldehyde sensor of double-decker and its preparation side
Method, it is possible to increase the sensitivity of formaldehyde sensor.
The technical solution adopted by the present invention is as follows：
The photocatalysis formula formaldehyde sensor of a kind of double-decker, it is characterised in that including light source, electrode, formaldehyde sensitivity material
The bed of material and methyl aldehyde adsorption material layer, on the electrodes, the methyl aldehyde adsorption material layer covers for the formaldehyde sensitive material covering
Cover on the formaldehyde sensitive material.
Further, the position of the light source is advisable with that can irradiate the formaldehyde sensitive material.Such as by light
Source is arranged on methyl aldehyde adsorption material layer side, and methyl aldehyde adsorption material layer has translucency, and the light that light source is sent passes through formaldehyde absorbing
Material layer reaches formaldehyde sensitive material.Or light source is arranged on formaldehyde sensitive material side, formaldehyde described in direct irradiation
Sensitive material.Now to avoid electrode part by photo-electric switch, the transparency electrode that can pass through ultraviolet light can be used.
Further, the formaldehyde sensitive material is cadmium (Cd) doped zinc oxide nano particle, the formaldehyde absorbing material
The bed of material is porous oxidation nano silicon particles.
Further, the thickness of the formaldehyde sensitive material is 5 microns~100 microns, the methyl aldehyde adsorption material layer
Thickness be 1 micron~50 microns.
Further, the light source is ultraviolet source, for example the ultraviolet lamp tube of 365nm wavelength or 385nm wavelength is ultraviolet
Light emitting diode；The electrode is interdigital electrode, array electrode or band electrode.
A kind of method for the photocatalysis formula formaldehyde sensor for preparing above-mentioned double-decker, its step include：
1) cadmium doped zinc oxide nano particle is synthesized：Zinc oxide nanoparticle well prepared in advance is immersed in cadmium salt soln
In, then heating makes solvent volatilize, and heating makes sample drying, and then sample is calcined, is ground into sample after calcining
Fine powder simultaneously forms slurry with ethanol is scattered；
2) synthesizing porous silica nano particle：By water, ethanol, CATC (hexadecyltrimethylammonium chloride), DEA (two
Monoethanolamine) mix and heat in a water bath, it is added to by way of then TEOS (tetraethyl orthosilicate) is stirred while being added dropwise
In mixture, continue product is distributed in ethanol to form sol dispersion after stirring certain time；
3) the cadmium doping zinc-oxide slurry for preparing step 1) is coated on electrode, and drying makes solvent volatilize, then
The sol dispersion of porous silica prepared by step 2) is coated on cadmium doping zinc-oxide layer, and drying waves solvent
Hair, then increase light source and formaldehyde sensor is made.When detecting formaldehyde, with ultraviolet source irradiation double-decker region, sensor
Resistance variations under ultraviolet source irradiation can be used for the concentration for calculating formaldehyde.
Further, after Zinc oxide nanoparticle is immersed in cadmium salt soln by step 1), be warming up to 70~90 DEG C make it is molten
Agent is volatilized, and heating heating in 10~14 hours and 110~130 DEG C makes sample drying in 1~3 hour at such a temperature, then by sample
Product are calcined 400~500 DEG C (being preferably 450 DEG C).
Further, step 2) heats 20~40 minutes after the mixing in 50~70 DEG C of water-baths；By positive silicic acid
Ethyl ester continues stirring 1~3 hour after being added in mixture.
Cadmium doping zinc-oxide formaldehyde sensor greatly improved for low concentration formaldehyde by the method for simplicity in the present invention
Sensitivity, the practical progress of the sensor is promoted, has been had a good application prospect.
Brief description of the drawings
Fig. 1 is the formaldehyde sensor structural representation of the present invention.
Fig. 2 is currently preferred sensor double-decker partial schematic diagram.
Fig. 3 is double-decker sensor production step schematic diagram.
Fig. 4 is porous oxidation nano silicon particles (sample size 5mg, test container 1L) Static Adsorptive capacity figure..
Fig. 5 is for formaldehyde sensitivity after coating porous oxidation nano silicon particles, ZIF-8 and active carbon adsorption material layer
Comparison diagram.
Fig. 6 is cadmium doping zinc-oxide sensor and adds the formaldehyde sensitivity curve pair of porous silica coating sensor
Than figure.
Embodiment
In order to facilitate the understanding of the purposes, features and advantages of the present invention, below by specific embodiment and
Accompanying drawing, the present invention will be further described.
Due to the serious indoor decoration pollution problem of China, it is badly in need of the formaldehyde sensor production of a kind of low cost, high selectivity
Product.The present invention provides a kind of photocatalysis formula formaldehyde sensor with double-decker.As shown in figure 1, the sensor include light source,
Electrode and double-deck material coating structure.The formaldehyde sensitive material that the double-decker includes one layer of photocatalysis principle directly covers
On electrode, and a methyl aldehyde adsorption material layer is covered on formaldehyde sensitive material.Light source is ultraviolet source, is irradiated to this
Double-decker region.When detecting the formaldehyde pollutants in air, the methyl aldehyde adsorption material layer can increase formaldehyde sensitive material
The concentration of formaldehyde of layer surface, so as to realize the effect of increase sensor sensitivity, i.e., it can improve the spirit for low concentration formaldehyde
Sensitivity.
As shown in Fig. 2 formaldehyde sensitive material is preferably using sensitive cadmium (Cd) the doping oxidation of PARA FORMALDEHYDE PRILLS(91,95) in the sensor
Zinc nanoparticles, methyl aldehyde adsorption material layer preferably use porous oxidation nano silicon particles, and electrode can use interdigital electrode etc..Should
Methyl aldehyde adsorption material layer has the characteristics that：1. there is adsorption capacity for formaldehyde；2. (can be by ultraviolet with translucency
Light), the light that light source is sent can be made to pass through sorbing material to reach sensitive material；3. for the characteristic of semiconductor bag of sensitive material
Electric property, photoelectric properties etc. are included not have a negative impact.The present invention tests a variety of suctions for formaldehyde with adsorption capacity
Enclosure material, including：Porous silica, activated carbon, carbon black, ZIF-8 etc..Wherein there was only porous oxidation nano silicon particles for sensing
The formaldehyde examination of device has positive effect, and its reason is that porous oxidation nano silicon particles have These characteristics.Need
Bright, light source can also be arranged on formaldehyde sensitive material side by the present invention, with formaldehyde sensitive material described in direct irradiation.
Now to avoid electrode part by photo-electric switch, the transparency electrode that can pass through ultraviolet light can be used.
The double-decker sensor production step of the present invention was prepared as shown in figure 3, being illustrated below by embodiment
Journey.
Embodiment 1：
Step 1：The synthesis of Zinc oxide nanoparticle
By 10.77g ZnSO4·7H2O (375mmol) is dissolved in 25mL deionized waters.Solution is added dropwise to
50mL100g/L(1.36mmol/L)NH4HCO3In solution, 1h is stirred under 40 DEG C of water-baths.Remove supernatant, gone every time with 15mL
Ion water washing precipitates, and washing altogether three times, then will be deposited in 80 DEG C of dry 12h, in 120 DEG C of dry 2h.By sample after having dried
It is put into 500 DEG C of calcining 2h in Muffle furnace.
Step 2：The addition of cadmium element
Weigh the previously prepared Zinc oxide nanoparticles of 0.4g and be dispersed in (3CdSO in 60mL cadmium salt solns4·
8H2O0.019g), solution stirs simultaneously solvent evaporated at 80 DEG C, 80 DEG C of dry 12h will be then deposited in, in 120 DEG C of dry 2h.
It will be deposited at 450 DEG C and calcine after this.
Step 3：The synthesis of porous oxidation nano silicon particles
The CATC (hexadecyltrimethylammonium chloride) of 6.4mL water, 0.9g ethanol, 1.04g25% percentage by weights is molten
Liquid, 0.02gDEA (diethanol amine) are mixed and heated 30 minutes in 60 DEG C of water-baths.Then by 0.73mLTEOS (positive silicic acid second
Ester) while be added dropwise while stir by way of be added in mixture, then proceed to stir 2 hours.
Step 4：Sensitive material coats
The solid product that step 2 is obtained, which is ground to after micro mist to be dispersed in absolute ethyl alcohol, is made slurry, then will
Prepared slurry is coated with electrode, is dried up ethanol (1min) with hair dryer.
Step 5：Sorbing material layer coats
The product ethanol that step 3 obtains is disperseed sol dispersion is made, is then coated with resulting dispersion liquid
On sensitive material obtained by step 4, electricity consumption blowing is dried up to form double-decker.
Step 6：Formaldehyde examination
Ultraviolet source produces photocatalytic effect, the detection for formaldehyde for sensitive material.The ultraviolet lamp tube of 365nm wavelength
Or the UV LED of 385nm wavelength can be used as ultraviolet source.When ultraviolet source is opened, due to zinc oxide material
The photic conductance effect of material, the resistance of sensor start to reduce.After certain time (being typically 5 minutes), resistance value reaches
It is stable.When in the air of cleaning, the resistance value is set to R0.When sensor is transferred to the sky containing formaldehyde from the air of cleaning
When in gas, reduction occurs in the resistance value of sensor.After the regular hour (being typically 3 minutes), resistance value reaches stable,
And it is set to Rs.According to predetermined relation, the concentration of formaldehyde can be by Rs/R0It is calculated.After detection is completed, by
There is dismantling-cleaning effect for the formaldehyde adsorbed on sensor material in photocatalysis effect, the resistance value of the sensor can be certainly
It is dynamic to return back to R0。
The Static Adsorptive capacity curve of porous oxidation nano silicon particles is as shown in figure 4,5mg porous oxidation nano silicon particles samples
Absorption of the product in 1L containers for formaldehyde reaches balance in 200s or so.
Porous oxidation nano silicon particles, ZIF-8 and charcoal absorption is respectively coated mixing cadmium Zinc oxide nanoparticle surface
It is as shown in Figure 5 for the contrast of formaldehyde sensitivity after material layer.It can be seen that mix cadmium compared to do not increase sorbing material coating
Zinc oxide nanoparticle, coat sensitivity of the sample of porous oxidation nano silicon particles for 3ppm formaldehyde and brought up to from 30%
45%.And ZIF-8 and the sample of activated carbon coating all cause the sensitivity of sensor to be greatly reduced.It is because while ZIF-8
There is adsorption capacity for formaldehyde with activated carbon, but the two can hinder ultraviolet lighting to be mapped to sensitive material, and for oxidation
The photoelectric properties of zinc in itself have negative effect.
Fig. 6 is cadmium doping zinc-oxide sensor and adds the formaldehyde sensitivity curve pair of porous silica coating sensor
Than figure, its abscissa is concentration of formaldehyde, and ordinate is for resistance of the sensor in containing formaldehyde air and in clean air
The ratio R of resistances/R0。Rs/R0Numerical value it is smaller, illustrate that the sensitivity for formaldehyde is higher.As can be seen that in same formaldehyde
Under concentration, the transducer sensitivity of porous oxidation silicon coating is added apparently higher than not having cated cadmium doping zinc-oxide to sense
Device.
Embodiment 2：
The method of step 2 could alternatively be following scheme in embodiment 1：
Step 2：The addition of cadmium element
Weigh the previously prepared Zinc oxide nanoparticles of 0.4g and be dispersed in (3CdSO in 60mL cadmium salt solns4·
8H2O0.019g), solution stirs simultaneously solvent evaporated at 70 DEG C, 70 DEG C of dry 10h will be then deposited in, in 110 DEG C of dry 1h.
It will be deposited at 400 DEG C and calcine after this.
Embodiment 3：
The method of step 2 could alternatively be following scheme in embodiment 1：
Step 2：The addition of cadmium element
Weigh the previously prepared Zinc oxide nanoparticles of 0.4g and be dispersed in (3CdSO in 60mL cadmium salt solns4·
8H2O0.019g), solution stirs simultaneously solvent evaporated at 90 DEG C, 90 DEG C of dry 14h will be then deposited in, in 130 DEG C of dry 3h.
It will be deposited at 500 DEG C and calcine after this.
Embodiment 4：
The method of step 3 could alternatively be following scheme in embodiment 1：
Step 3：The synthesis of porous oxidation nano silicon particles
The CATC (hexadecyltrimethylammonium chloride) of 6.4mL water, 0.9g ethanol, 1.04g25% percentage by weights is molten
Liquid, 0.02gDEA (diethanol amine) are mixed and heated 20 minutes in 50 DEG C of water-baths.Then by 0.73mLTEOS (positive silicic acid second
Ester) while be added dropwise while stir by way of be added in mixture, then proceed to stir 1 hour.
Embodiment 5：
The method of step 3 could alternatively be following scheme in embodiment 1：
Step 3：The synthesis of porous oxidation nano silicon particles
The CATC (hexadecyltrimethylammonium chloride) of 6.4mL water, 0.9g ethanol, 1.04g25% percentage by weights is molten
Liquid, 0.02gDEA (diethanol amine) are mixed and heated 40 minutes in 70 DEG C of water-baths.Then by 0.73mLTEOS (positive silicic acid second
Ester) while be added dropwise while stir by way of be added in mixture, then proceed to stir 3 hours.
The above embodiments are merely illustrative of the technical solutions of the present invention rather than is limited, the ordinary skill of this area
Technical scheme can be modified by personnel or equivalent substitution, without departing from the spirit and scope of the present invention, this
The protection domain of invention should be to be defined described in claims.
Claims (9)
1. the photocatalysis formula formaldehyde sensor of a kind of double-decker, it is characterised in that including light source, electrode, formaldehyde sensitive material
Layer and methyl aldehyde adsorption material layer, on the electrodes, the methyl aldehyde adsorption material layer covers for the formaldehyde sensitive material covering
On the formaldehyde sensitive material；The formaldehyde sensitive material is cadmium doped zinc oxide nano particle, the formaldehyde absorbing
Material layer is porous oxidation nano silicon particles；The formaldehyde sensitive material layer surface is increased by the methyl aldehyde adsorption material layer
Concentration of formaldehyde, so as to increase the sensitivity of formaldehyde sensor PARA FORMALDEHYDE PRILLS(91,95).
2. the photocatalysis formula formaldehyde sensor of double-decker as claimed in claim 1, it is characterised in that：The light source is arranged on
The methyl aldehyde adsorption material layer side, the methyl aldehyde adsorption material layer have translucency, and the light that the light source is sent passes through described
Methyl aldehyde adsorption material layer reaches the formaldehyde sensitive material.
3. the photocatalysis formula formaldehyde sensor of double-decker as claimed in claim 1, it is characterised in that：The light source is arranged on
The formaldehyde sensitive material side, formaldehyde sensitive material described in direct irradiation.
4. the photocatalysis formula formaldehyde sensor of double-decker as claimed in claim 1, it is characterised in that：The formaldehyde sensitivity material
The thickness of the bed of material is 5~100 microns, and the thickness of the methyl aldehyde adsorption material layer is 1~50 micron.
5. the photocatalysis formula formaldehyde sensor of double-decker as claimed in claim 1, it is characterised in that：The light source is ultraviolet
Light source, the electrode are interdigital electrode, array electrode or band electrode.
6. the photocatalysis formula formaldehyde sensor of double-decker as claimed in claim 5, it is characterised in that：The ultraviolet source is
The ultraviolet lamp tube of 365nm wavelength or the UV LED of 385nm wavelength.
7. a kind of method for the photocatalysis formula formaldehyde sensor for preparing double-decker described in claim 1, its step include：
1) Zinc oxide nanoparticle well prepared in advance is immersed in cadmium salt soln, then heating makes solvent volatilize, and heats
Make sample drying, then sample is calcined, sample is ground into fine powder after calcining and forms slurry with ethanol is scattered；
2) water, ethanol, hexadecyltrimethylammonium chloride, diethanol amine are mixed and heated in a water bath, then by positive silicic acid
Ethyl ester is added in mixture by way of being stirred while being added dropwise, and continues that product is distributed in ethanol after stirring certain time
Form sol dispersion；
3) the cadmium doping zinc-oxide slurry for preparing step 1) is coated on electrode, and drying makes solvent volatilize, then will step
The sol dispersion of the rapid porous silica 2) prepared is coated on cadmium doping zinc-oxide, and drying makes solvent volatilize, then
Formaldehyde sensor is made in increase light source.
8. method as claimed in claim 7, it is characterised in that：Zinc oxide nanoparticle is immersed in cadmium salt soln by step 1)
Afterwards, being warming up to 70~90 DEG C makes solvent volatilize, and heats at such a temperature 10~14 hours, then heats 1 at 110~130 DEG C
Make sample drying within~3 hours, then calcined sample at 400~500 DEG C.
9. method as claimed in claim 7, it is characterised in that：Step 2) is after the mixing, in 50~70 DEG C of water-baths
Heating 20~40 minutes；Continue stirring after tetraethyl orthosilicate is added in mixture 1~3 hour.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510208449.1A CN104897735B (en) | 2015-04-28 | 2015-04-28 | A kind of photocatalysis formula formaldehyde sensor of double-decker and preparation method thereof |
| JP2016059182A JP6239668B2 (en) | 2015-04-28 | 2016-03-23 | Double-layer photocatalytic formaldehyde sensor and manufacturing method thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510208449.1A CN104897735B (en) | 2015-04-28 | 2015-04-28 | A kind of photocatalysis formula formaldehyde sensor of double-decker and preparation method thereof |
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| CN104897735A CN104897735A (en) | 2015-09-09 |
| CN104897735B true CN104897735B (en) | 2017-12-19 |
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| CN105136863B (en) * | 2015-09-11 | 2018-02-06 | 云南大学 | Based on CdIn2O4The gas sensor and preparation method of nano thin-film |
| CN105866183B (en) * | 2016-03-11 | 2019-03-22 | 北京大学 | A kind of formaldehyde sensitive material of La doped and preparation method thereof and formaldehyde sensor |
| CN108426979B (en) * | 2017-09-08 | 2020-09-29 | 重庆邮电大学 | Gas/liquid safety detection unit |
| CN109030564B (en) * | 2018-06-04 | 2021-05-11 | 深圳大学 | Transistor type formaldehyde sensor and manufacturing method thereof |
| CN110726760B (en) * | 2019-10-23 | 2020-08-11 | 山东交通学院 | Ship mechanism with tail gas sensing device |
| CN111537570A (en) * | 2019-12-20 | 2020-08-14 | 湘潭大学 | Holmium ferrite formaldehyde gas sensor based on red light auxiliary mode |
| CN112179956B (en) * | 2020-09-29 | 2021-11-19 | 西安交通大学 | Preparation method of MEMS formaldehyde sensor based on aluminum-doped zinc oxide porous nano film |
| CN114624292A (en) * | 2020-12-12 | 2022-06-14 | 中国科学院大连化学物理研究所 | VOCs sensor and preparation method thereof |
| CN114720521A (en) * | 2022-03-30 | 2022-07-08 | 辽宁大学 | Cd (cadmium)2+Preparation method of ZnO formaldehyde gas sensor material with ion adsorption function |
| CN114813858A (en) * | 2022-05-11 | 2022-07-29 | 吉林大学 | Formaldehyde gas sensor based on neodymium oxide modified indium trioxide rod-shaped composite material and preparation method thereof |
| CN117571794B (en) * | 2024-01-15 | 2024-03-19 | 电子科技大学中山学院 | Laser enhancement type zinc oxide formaldehyde detection device |
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| Title |
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| "氧化锌纳米复合材料的光电气敏性质研究";翟佳丽;《中国博士学位论文全文数据库 工程科技I辑》;20120915(第9期);第41页图2.2、2.3，第43页第2.1.3节，第47页第2.2.3节 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104897735A (en) | 2015-09-09 |
| JP6239668B2 (en) | 2017-11-29 |
| JP2016212087A (en) | 2016-12-15 |
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